Some photoeffects on the semiconductor surface under sub-bandgap illumination

Surface photovoltage as well as surface photoconductivity response on the light intensity under sub-bandgap illumination is treated. The influence of the surface barrier height, the density of surface traps, the bulk electron density as well the temperature on the surface photovoltage (surface photoconductivity) is analysed. The detectability conditions are included. The consequences of detectability conditions are discussed.     

Photoelectricity of β-Agl under sub-bandgap illumination

An experimental study of the spectral, intensity and temperature dependences of the photoconductivity and contact photovoltage of β-AgI single crystals under sub-bandgap illumination is carried out. Both dc and ac photoconductivity experiments are performed and dark-to-light relaxation characteristics of the contact photovoltage are investigated. It is found that the processes under consideration are of a unified character in the spectral region below 2.20 eV, in which the photoconductivity spectrum follows Urbach's rule, temperature behaviour is opposite to that of dark conductivity and dependence on exciting light intensity is linear. A simple model is proposed to explain qualitatively the results obtained, based on the assumption for photoexcited ionic-type conductivity.     

Phonons in surface photovoltage of GaAs

Oscillatory surface photovoltage is reported in GaAs at 4.2°K, characterized by two series of minima. Dominating series is attributed to the capture of photoexcited electrons by surface states with emission of phonons. Second, weak series coincides with oscillations in photoconductivity.     

The influence of light intensity on surface recombination in GaS single crystals

Gallium sulphide (GaS) is a layer structure semiconductor with relatively wide energy gap (E_g (295 K) = 2.5 eV and E_g (80 K) = 2.62 eV). It has potential applications in some areas of optoelectronics. This paper presents the investigations of the influence of light intensity on surface recombination velocity of charge carriers in GaS single crystals. To attain this purpose spectral dependences (between 420 and 550 nm) of absorption coefficients, reflectivity coefficients and photoconductivity were measured in vacuum. The investigations were performed for various light intensities in several temperatures from 80 to 333 K. The least square method was applied to fit the theoretical dependences of photoconductivity on wavelength and intensity of illumination at these temperatures. From the fittings the temperature and light intensity dependences of surface recombination velocity and bulk lifetime of charge carriers were obtained.     

Optical spectroscopy of electronic surface states

In this paper a number of optical spectroscopic methods for investigating surface electronic structure are discussed, including reflectance techniques, ellipsometry, surface photoconductivity and surface photovoltage spectroscopy. In addition to electron scattering techniques and UV-photoemission, optical spectroscopic methods have contributed much in recent times to the understanding of electronic surface states on solids. A discussion and comparison is given of the nature and significance of information obtained by these methods and exemplary experimental results are presented to illustrate the contribution of the optical techniques to the present knowledge about surface states. The relation between information obtained from optical measurements and electron spectroscopy is considered.     

Photoreflection and photoconduction spectra of CdS crystals: Excitons in the electric fields of surface states

The exciton photoreflection spectra of CdS crystals are studied. It is found that the form of the exciton photoreflection spectrum is determined by a Stark shift of the exciton energy in the electric field of surface states. The dependences of the exciton photoreflection spectrum on temperature on the intensity and wavelength of the modulating radiation, and on the processes by which the photoreflection signal relaxes is determined. An energy scheme is proposed for the surface states which explains the observed effects of photoinduced changes in the surface field. A correlation is established between the exciton photoreflection spectrum and the form of the fine structure in the photoconductivity. Fiz. Tverd. Tela (St. Petersburg) 40, 875–876 (May 1998)     

Surface state properties of clean cleaved silicon as derived from the temperature dependence of the surface photovoltage

The temperature dependence of the surface photovoltage of clean silicon surfaces cleaved in UHV was investigated with a special emphasize on that temperature where surface photovoltage changes its sign. The surface photovoltage was measured by the electron beam method. Chopped light with an energy larger than the bandgap of silicon was used. The ratio of the transition probabilities $\text{r}{}_{\mathrm{V}}\text{r}{}_{\mathrm{C}}$ for transitions from and into the surface states has been derived from the surface photovoltage and the value for the band bending at the clean silicon surface. It is concluded from model calculations that at temperatures below the sign change of the surface photovoltage the signal height of the surface photovoltage is essentially determined by the surface recombination whereas the contribution due to band bending is negligible.     

Photovoltaic properties of a heterojunction based on copper phthalocyanine films on the surface of polycrystalline cadmium sulfide

The photovoltaic effect has been detected and studied in thin-film structures based on thermally deposited 200-nm-thick copper phthalocyanine (CuPc) films on the surface of polycrystalline CdS. The structures under study demonstrate the linear current-voltage characteristics at external electric fields to 3.5 × 10⁴ V/cm. Two components of the photovoltage of different signs have been revealed when the sample is illuminated in the wavelength range from 350 to 700 nm. The first component has the positive sign on the CuPc film side and is observed when using the radiation with a wavelength lesser than 500 nm, i.e., in conditions of predominant absorption of the radiation in the CdS layer. The second component has the negative sign on the CuPc film side and is observed when using the radiation with a wavelength in the range from 500 to 570 nm, corresponding to the spectral region of the absorption edge of the CuPc films. The dependences of the photovoltage on the radiation intensity studied in the range from 5 × 10¹² to 10¹⁴ photons cm^?2 s^?1 are different in the cases of the two detected components. Mechanisms of generation of the photovoltage components associated with a change in the band bending during photogeneration of charge carriers in the region of space charge in CdS and a change in conditions of the charge transfer in the interfacial CuPc/CdS region during the radiation absorption in the CuPc film have been proposed.     

Non-equilibrium surface state properties at clean cleaved silicon surface as measured by surface photovoltage

Surface photovoltage transients were measured at clean cleaved silicon (111) faces in ultrahigh vacuum. The temperature and doping of the samples, the intensity of the stimulating light pulses (energy less than band gap), and the surface coverage (clean and adsorbed water vapor) were varied systematically. The results yield information on the charge transfer at the surface and on surface recombination. The calculation of the surface photovoltage (using only the generation rates into and out of the surface states and data of thermal equilibrium) shows, that only one bulk band (conduction band for n-doped samples and valence band for p-doped samples) controls completely signal height and its relaxation via charge transfer to the surface states. The determined surface state parameters are: relaxation time constants, capture cross-sections for photons and transition probabilities. On the basis of the model all decay curves can be reproduced quantitatively.     

Investigation on electronic transitions in Co-doped ZnO by surface photovoltage spectra

Surface photovoltage spectrum (SPS) technique is one of the powerful experimental methods for studying the attribution of electronic transition. The SPS investigation on Zn_0.97Co_0.03O system has been reported here. The different transitions in the material are distinguished by the electric field-induced surface photovoltage spectra (EFISPS), in which SPS is combined with the electric field-modified technique. The presence of the interaction between defects (excitonic transition) and Co²⁺ (charge-transfer transition) is confirmed by EFISPS. The magnetic properties are measured as a function of magnetic field and temperature. No hysteresis is observed, but Curie–Weiss temperature for Co-doped ZnO is positive.     

The influence of atomic steps on the photoelectric properties of clean cleaved silicon as derived from the surface photovoltage

The correlation of structural and electrical properties of clean silicon surfaces cleaved in UHV was investigated quantitatively by the surface photovoltage, using light with an energy larger than the band gap of silicon. The surface photovoltage, which is a function of band bending and recombination probability, depends strongly on the appearance of atomic steps. The additional surface states vary with density and crystallographic orientation of the steps as well as with adsorption of oxygen. The experimental facts can be explained by accepting a shift of the Fermi level at the surface towards the valence band due to edge atoms. By measuring the change of sign of the surface photovoltage of crystals with various dopings an exponential temperature dependence of the ratio of the recombination probabilities r_v/r_c for transitions from and into the Surface states has been derived.     

Surface photovoltage and internal photoemission at the anodized InSb surface

Surface photovoltage measurements have been made as a function of wavelength and temperature on a number of variously doped samples of n- and p-type InSb in the carrier concentration range of 8.9 × 10¹³ to 1.0 × 10¹⁸ cm^?3. The measurements were made using an MIS sandwich employing for the dielectric an anodically formed layer of In₂ O₃. Differential capacitance measurements have shown that, when cooled in the dark, the surface of the n-type material is near flat band whereas that of the p-type is depleted. Illumination with photons of energy in excess of ～ 1.5 eV leads to a shift of the surface potential to larger negative values presumably as a result of optical activation of electrons from fast interfacial surface states to slow states near the InSb surface. Internal photoemission measurements lend support to this model and suggest that, in the absence of any applied bias an internal field within the oxide causes the electrons excited from the semiconductor to move towards the metal. A theory for the surface photovoltage in the presence of a continuum of surface states is developed. It is concluded from theory, and supported by experiment, that surface trapping as well as recombination can exert a considerable influence on the photovoltaic response.     

Surface photovoltage,band-bending and surface states on a-Si : H

We have measured the surface photovoltage (SPV) of intrinsic (i.e., undoped) and phosphorus-doped amorphous Si : H between ?168 and 25°C in the spectral range from 0.5 to 2.5 eV. The a-Si : H was grown in a silane glow discharge. Vibrating Kelvin probe techniques were used for the SPV measurements; Auger spectroscopy was used for monitoring surface cleanliness and chemistry. At all temperatures and for both materials, (1) the SPV was invariably negative, (2) there was no correlation between the spectral, thermal and response-time properties of the SPV and the bulk photoconductivity, and (3) surface treatments such as sputtering and oxygen physisorption strongly affected the SPV but not the photoconductivity. These facts indicated that the SPV was due to the emptying of surface-states via surface transitions, and corresponded to the flattening of bands which, when unilluminated, were bent upwards. Intrinsic material showed a maximum SPV of about 0.2 V. The SPV was characterized at ?168°C by strong electronic isolation between surface-states and valence band (i.e., once light was removed, there was no surface-state refilling or decay of the SPV), slow rise times (～min), saturation at photon fluxes of about 10¹¹/cm² · s, and a SPV spectral threshold occurring at 0.7 eV. At 25°C, all SPV responses were much faster (<0.5 s) and the optical threshold was 0.9 eV. The thermal activation energies associated with the SPV were 0.11 eV for surface-state emptying and 0.22 eV for surface-state refilling. For P-doped material the maximum SPV at ?168°C was 0.3 V and its properties indicated less electronic isolation between surface-states and valence band. There was no SPV at room temperature. Our results are discussed in terms of an energy level scheme which contains a distribution of filled surface states isolated from both conduction and valence bands. The surface-state density is estimated to be about (1?2) × 10¹¹/ cm², a relatively low value which is consistent with the observed lack of Fermi level pinning. In both materials there is a very fast component of the SPV which suggests the presence of additional surface states below the valence band edge.     

ZnO/Si异质结的光电转换特性研究

利用直流反应溅射方法在p型Si衬底上生长掺Al的n型ZnO薄膜,测量了由n型ZnO薄膜和p型Si衬底组成的异质结在黑暗和光照条件下的I-V特性,结果表明该异质结具有优良的整流特性,而且在光照条件下的反向电流迅速增大并很快趋于饱和.通过测量ZnO薄膜的光电流和异质结的光电压的光谱响应,初步分析了异质结的光电转换机理.测量结果显示,在入射光波长为380nm时光电流强度明显下降,反映出光电流与ZnO薄膜禁带宽度的密切关系;同时还发现,在与ZnO禁带宽度相对应的波长前后所产生的光生电压方向相反.推测这一现象与异质结的能带结构密切相关. 关键词： ZnO薄膜 异质结 光电转换 光谱响应     

Photovoltage studies of n-type InP (100)

The transient photovoltage signals of n-type InP(100) have been studied by the retarding potential electron beam technique and are a sensitive function of several experimental parameters. The photovoltage decreases as the duration of the light exposure, and/or the intensity of the light is decreased. The photovoltage decreases sharply at energies less than the bandgap energy, which is temperature dependent, and also shows considerable structure at energies above the bandgap energy. The photovoltage is also sensitive to changes in the surface composition. Both the photovoltage and the work function decrease sharply after Ar bombardment.     

On the correlation of geometrical structure and electronic properties at clean semiconductor surfaces

In their LEED patterns most clean semiconductor surfaces show extra spots in addition to the normal beams as expected for a continuation of the bulk lattice up to the topmost layer. This means, that these surfaces are reconstructed. The (111) surfaces of silicon and germanium crystals exhibit another interesting feature: the cleaved surfaces show a metastable superstructure which irreversibly converts to a new modification upon heat treatments above about $\text{1}\text{3}$ of the melting temperatures. The structural changes are correlated with changes in the electronic properties of the surfaces. This has been shown by investigations of surface conductivity, surface photoconductivity, surface photovoltage, internal reflection, electron energy-loss spectroscopy, photoemission, and work function. Recent theoretical studies have also revealed a distinct correlation between geometrical arrangements of the surface atoms and the corresponding band structures of the surface states. However, the atomic positions of the surface atoms used in these calculations are only a model since a detailed analysis of the LEED-intensity-versus-energy curves have not been carried out up to now.     

Features of the electrical and photoelectrical properties of nanocrystalline indium and zinc oxide films

Electrical and photoelectrical properties of nanocrystalline zinc oxide and indium oxide films are studied. For these oxides the temperature dependences of conductance are observed to be consisting of two parts with different activation energy. Also photoconductivity relaxation of the oxides can be described by a sum of two exponential functions. The spectral dependencies of nanocrystalline zinc oxide and indium oxide photoconductivity are presented. The photoconductivity arises as samples are illuminated with energy less than band gap. The data are discussed on the basis of model by which the localized states in the band gap play major role.     

Photoconductivity and photovoltaic behaviour of LiNbO3 and LiNbO3 waveguides at high optical intensities

The photoconductivity and photovoltaic currents of pure LiNbO₃ and proton exchanged waveguides in LiNbO₃ have been measured as a function of the optical intensity up to about several kW/cm² by the use of surface electrodes. For pure LiNbO₃ the observed dependences are a simple extrapolation of the well known low intensity behaviour. The photoconductivity of proton exchanged waveguides is considerably increased compared with pure LiNbO₃ and the curves are strongly nonlinear in the high intensity region. These results can explain, at least qualitatively, the previously observed characteristic time and intensity dependence of light-induced refractive index changes in this type of waveguides. Both the time and temperature behaviour of the dark conductivity of all proton exchanged waveguides give strong evidence of ionic charge transport in the proton exchanged region.     

Photoelectronic properties of organic films on the silicon surface

The photoelectronic properties of organic semiconductor-silicon heterostructures (such as PTCDA-Si, CuPc-Si, and OPV-Si) are investigated. The I-V characteristics, as well as the spectral dependences of photoconductivity and photoinduced potential, are measured. Photosensitivity is observed in the absorption bands of both silicon and the organic films. A maximum potential (up to 0.25 V) is observed for the PTCDA-Si heterojunctions. In the OPV-Si heterojunction, the photoinduced potential changes sign under illumination at different wavelengths in the optical range.     

Sensitization of ZnO photoconductivity by chemical modification of surface states

Surface States on ZnO have been investigated through their effect on photoconductivity. Low energy photons (0·7 ～ 1·5 eV) are found to induce a feeble photocurrent in ZnO which is attributable to the direct electron injection from surface levels to the conduction band. A definite correlation has been found between the i.r. induced photocurrent and the intrinsic or the dye sensitized photocurrent excited by UV or visible radiation. It is proposed that phthalic anhydride on ZnO modifies the distribution of surface levels, by a chemical interaction with chemisorbed oxygen. Surface levels originating in chemisorbed oxygen ions are transformed by phthalic anhydride into new levels which are shallower but thermally more stable. These traps are found to enhance the photoconductivity of ZnO. The chemical nature of them and the mechanism of sensitization are discussed.